Chem Soc Rev

View Article Online

TUTORIAL REVIEW View Journal | View Issue

Fabrication of desalination membranes by

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

interfacial polymerization: history, current efforts,

Cite this: Chem. Soc. Rev., 2021,
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

50, 6290 and future directions

ab
Xinglin Lu and Menachem Elimelech *b

Received 19th January 2021
DOI: 10.1039/d0cs00502a
rsc.li/chem-soc-rev
Membrane desalination is a promising technology for addressing the global challenge of water scarcity
by augmenting fresh water supply. Continuous progress in this technology relies on development of
membrane materials. The state-of-the-art membranes used in a wide range of desalination applications
are polyamide thin-film composite (TFC) membranes which are formed by interfacial polymerization (IP).
Despite the wide use of such membranes in desalination, their real-world application is still hampered
by several technical obstacles. These challenges of the TFC membranes largely stem from the inherent
limitations of the polyamide chemistry, as well as the IP reaction mechanisms. In the past decade, we
have witnessed substantial progress in the understanding of polyamide formation mechanisms and the
development of new IP strategies that can potentially lead to the redesign of TFC membranes. In this
Tutorial, we first present a brief history of the development of desalination membranes and highlight the
major challenges of the existing TFC membranes. We then proceed to discuss the pros and cons of
emerging IP-based fabrication strategies aiming at improving the performance of TFC membranes. Next,
we present technical obstacles and recent efforts in the characterization of TFC membranes to enable
fundamental understanding of relevant mechanisms. We conclude with a discussion of the current gap
between industrial needs and academic research in designing high-performance TFC membranes, and
provide an outlook on future research directions for advancing IP-based fabrication processes.

Key learning points

(1) Current status of desalination processes and historical timeline for the development of desalination membranes.
(2) Major challenges of thin-film composite (TFC) membranes made by interfacial polymerization (IP) in desalination applications.
(3) Emerging strategies of IP for fabricating high-performance TFC membranes.
(4) Emerging techniques for polyamide thin-film characterization for revealing structural information of TFC membranes.
(5) Gap between industrial needs and academic research in designing high-performance TFC membranes, and potential research directions for advancing
IP-based fabrication processes.

1. Introduction is predicted to double in the coming decade. To address this global

Water is a precious resource, essential to humanity’s sustainability
and well-being.1 However, population growth, industrialization,
and water contamination have led to the pressing challenge of
water scarcity around the globe.2 Presently, over one billion people
do not have adequate access to safe drinking water, and this figure
a
CAS Key Laboratory of Urban Pollutant Conversion, Department of Environmental
Science and Engineering, University of Science and Technology of China,
Hefei 230026, China
b
Department of Chemical and Environmental Engineering, Yale University,
New Haven, Connecticut 06520-8286, USA. E-mail: menachem.elimelech@yale.edu
challenge, we need technological innovations to enable an efficient
and sustainable supply of fresh water.
Desalination can offer a steady supply of high-quality fresh
water through the treatment of seawater and brackish ground-
water. These saline waters account for 97.5% of the water sources
on our planet, making desalination an important solution to
addressing water scarcity on a global scale.3 To date, over 18 000
operational desalination plants provide B90 million m3 of fresh
water daily to meet the demand of 300 million people, a number
equivalent to the population of the United States.4
Growing interest in desalination has resulted in several
technologies, which can be largely classified into two

6290 | Chem. Soc. Rev., 2021, 50, 6290–6307 This journal is © The Royal Society of Chemistry 2021
 View Article Online

Tutorial Review Chem Soc Rev

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

Fig. 1 Overview of the development and current status of desalination processes. (A) Trends in global desalination capacity in the past decades. (B) Share
of operational facilities using different technologies, including reverse osmosis (RO), nanofiltration (NF), multi-stage flash (MSF), and multi-effect
distillation (MED). Figures are reproduced with permission from ref. 6, Elsevier.

categories: thermal-based processes and filtration-based
processes. Thermal-based processes exploit a thermal-driven
phase change to separate water from non-volatile contaminants
like salt. These processes, such as multi-effect distillation
(MED) and multi-stage flash (MSF), were widely employed in
the Gulf countries before the 1990s (Fig. 1A). Filtration-based
processes, including reverse osmosis (RO) or nanofiltration
(NF), rely on external pressure to drive water molecules across
a semi-permeable membrane. Although both thermal-based
and filtration-based processes are effective in producing fresh
water, the intrinsic difference in driving force leads to different
separation principles and energy-consumption levels, which
were explained in a recent review article.5 In brief, thermal
desalination processes must overcome the enthalpy of vapor-
ization (i.e., latent heat, DHvap), while the filtration processes
must overcome the Gibbs free energy of separation (DGmix). To
produce a unit volume of fresh water under typical operating
conditions, DHvap is at least two orders of magnitude larger
than DGmix (667 vs. 1.06 kW h1 m3 for 50% water recovery).
As a result, filtration-based processes consume much less
energy than thermal-based processes in seawater desalination,
despite measures to recover the latent heat of vaporization in
thermal desalination technologies. Consequently, filtration-
based RO has become the predominant destination technology,
as illustrated by the rapid growth in the past two decades
(Fig. 1A), accounting for B70% of the global desalination
capacity (Fig. 1B).6
The development of the RO process has largely been governed
by advances in membrane materials, the core of the whole
process. A chronological summary of the evolution of the RO
desalination process is presented in Fig. 2 to illustrate the major
milestones in the development of this technology. While the
phenomenon of osmosis was first discovered in 1748, the proof-
of-concept of RO desalination was not demonstrated until two
centuries later, in the 1950s, using symmetric cellulose acetate
films.7 Despite good rejection of NaCl, the water flux of such
films was too low to be practically viable. Later, in the 1960s, two
pioneers—Loeb and Sourirajan—developed the first asymmetric
cellulose acetate (CA) membrane via phase separation.7 This
membrane exhibited high salt rejection with ten times larger

Xinglin Lu is a tenure-track Menachem Elimelech is the

assistant professor in the Sterling Professor of Chemical
Department of Environmental and Environmental Engineering
Science and Engineering at the at Yale University. His research
University of Science and interests include emerging
Technology of China (USTC). He membrane-based technologies at
received his PhD from Harbin the water-energy nexus, materials
Institute of Technology under for next generation desalination
the supervision of Prof. Jun Ma, and water purification
followed by postdoctoral training membranes, and environmental
in Prof. Menachem Elimelech’s applications of nanomaterials.
group at Yale University. He is Professor Elimelech is a
Xinglin Lu broadly interested in Menachem Elimelech Clarivate Analytics (formerly
technologies that hold potential Thomson Reuters) Highly Cited
in addressing challenges at the water-energy nexus. His current Researcher in two categories: chemistry and environment/ecology.
research focuses on advanced membrane materials and processes He is a member of the US National Academy of Engineering and a
for sustainable water supply and wastewater management. foreign member of the Chinese Academy of Engineering.

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 6290–6307 | 6291
 View Article Online

Chem Soc Rev Tutorial Review

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Fig. 2 Historical timeline of the development of membrane-based desalination processes.

Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

water flux than that of any available membranes, thereby facilitating
real-world applications of the RO process. Using this asymmetric
cellulose acetate membrane, the first pilot-scale RO system
was demonstrated in California in the 1960s, followed by the
establishment of the first RO municipal plants in Florida in the
1970s.7 These practical applications also enabled engineers and
researchers to realize the shortcomings of the cellulose-type
membranes in long-term operation, including a narrow operating
pH range and susceptibility to biological degradation. To
overcome these limitations, Cadotte developed the first thin-film
composite (TFC) polyamide membranes in the late 1970s.8
Compared with the cellulose acetate membranes, the TFC
membrane is characterized by exceptional desalination perfor-
mance (high water flux and high salt rejection) and enhanced
stability under a wider pH range, thereby becoming the gold
standard in RO-based desalination technologies.3
TFC membranes are fabricated through interfacial polymer-
ization (IP)—a process that allows for the facile synthesis
of an ultrathin selective layer. A representative procedure for
fabricating TFC RO membranes is illustrated in Fig. 3.
A microporous polysulfone membrane is first immersed in an
aqueous diamine solution, m-phenylenediamine (MPD), to
allow diamine penetration into the support. After removing
the excess diamine on the surface, the impregnated support is
brought into contact with an organic phase of acyl chloride—
trimesoyl chloride (TMC). As MPD monomers diffuse to the inter-
face between water and organic phases, they react with the TMC to
form a thin polyamide layer on top of the polysulfone support.
Although the advent of TFC membranes resulted in remarkable
energy savings in desalination, certain features of the fabrication
procedure and film properties are inherently limiting. For
example, the seemingly straightforward IP process turns out to
be rather complex, limiting the fundamental understanding of
polyamide formation mechanisms. As such, existing industrial
fabrication processes are largely empirical and lack molecular-level
design, leading to the formation of TFC membranes with
uncontrolled characteristics. Some membrane characteristics lead
to deleterious phenomena (e.g., fouling and low rejection of
neutral solutes) that are detrimental to product water quality
and system efficiency. Given the dominant role of TFC membranes
in RO desalination, there is a crucial need for a better mechanistic
understanding of the IP process to enable innovative designs and
to further advance RO desalination technologies.
Herein, we review the most recent progress in the IP process
towards the fabrication of high-performance TFC membranes.
We begin by highlighting the major limitations of TFC membranes
regarding their fabrication process and real-world applications. We
proceed to analyze the pros and cons of emerging IP-based
fabrication strategies that aim at improving the robustness of
TFC membranes. We then present technical obstacles and recent
efforts in the characterization of TFC membranes to enable
fundamental understanding of relevant mechanisms. Finally, we
discuss the current gap between industrial needs and academic
research in fabricating TFC membranes, and provide an outlook
on future research directions for advancing IP-based fabrication
processes.

Fig. 3 Schematic representation of a typical interfacial polymerization process for making TFC RO membranes. The reaction between m-phenylene-
diamine (MPD) and trimesoyl chloride (TMC) occurs at the surface of a microporous polysulfone support to form a thin polyamide layer, whose chemical
formula is illustrated. The m and n in the polymer structure represent the crosslinked and the linear segments, respectively (m + n = 1).

6292 | Chem. Soc. Rev., 2021, 50, 6290–6307 This journal is © The Royal Society of Chemistry 2021
 View Article Online

Tutorial Review Chem Soc Rev

2. Current challenges in fabricating Js = BDC (2)

high-performance TFC membranes
2.1. Breaking the trade-off between permeability and
selectivity
Mass transport in the dense, nonporous polyamide film of TFC
membranes is governed by the solution-diffusion model. Water
and solute molecules first partition into the polyamide layer,
diffuse through the polymer matrix under chemical potential
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
where B is the solute permeability coefficient and DC is the
concentration difference across the selective layer.
For a given membrane, the water and salt permeability
coefficients of the active layer are determined by the intrinsic
water permeability (Pw) and solute permeability (Ps), respectively:9
Pw Vw
A¼ (3)
dm Rg T

gradient, and desorb into the permeate side. Separation of

fresh water from saline water is achieved because of the Ps
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

difference in the permeabilities of water and solutes in the
polymer matrix. Water flux, Jw, is expressed as
Jw = A(DP  Dp)
where A is the water permeability coefficient (or permeance),
and DP and Dp are the applied pressure and osmotic pressure
differences across the active layer, respectively. Similarly, solute
flux, Js, is determined by
B¼ (4)
dm
where Vw is the molar volume of water, dm is the film thickness, Rg
(1) is the ideal gas constant, and T is the absolute temperature.
When plotting water–salt selectivity (Pw/Ps) versus water
permeability (Pw) in Fig. 4A, performance data of existing TFC
membranes are mostly confined in the blue-box region,
wherein the highest selectivity for a given permeability
approaches the solid line. This line represents the trade-off

Fig. 4 Major challenges of interfacial polymerization and TFC membranes. (A) Permeability–selectivity trade-off relationship for TFC desalination
membranes. Performance of current TFC membranes mostly lays in the blue box, in which the highest water–salt selectivity at a given water permeability
is near the indicated trade-off line. Ideal membranes would have both high permeability and high selectivity, thereby breaking the trade-off relationship
and laying in the top-right corner of the plot (red box). However, this combination is difficult to attain. A more practical strategy is to fabricate TFC
membranes with comparable water permeability of current membranes but with increased water–salt selectivity (green box); this strategy can improve
the efficiency of current desalination processes. (B) Correlation of crosslinking degree with salt rejection and permselectivity of TFC membranes.
(C) Surface characteristics that determine fouling propensity of TFC membranes. (D) Proposed mechanisms for the origin of the characteristic ridge-and-
valley structure of TFC membrane during interfacial polymerization: generation of interfacial instability in the organic phase and formation of nano-size
bubbles in the aqueous phase.

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 6290–6307 | 6293

Chem Soc Rev
relationship between permeability and selectivity, which is
widely observed in membrane processes using synthetic
polymer materials.10 Ideal membranes should have high values
of both water permeability and water–salt permselectivity
(i.e., the red-box region in Fig. 4A). Nevertheless, such a
combination is difficult to achieve, as most material properties
that affect water permeability would in turn exert similar effects
on solute permeability. Indeed, the influence of material
properties on salt permeability is more pronounced as salt
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
permeability is proportional to the cube of water permeability
(Ps p Pw3).9,11 That is, any increment in water permeability
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
would lead to an exponential increase in salt permeability and
thus a remarkable decrease in selectivity. Consequently, despite
substantial efforts in optimization of IP reaction conditions,
progress in pushing the trade-off line toward the ideal regime
(i.e., the red arrow in Fig. 4A) is relatively slow.
Instead of attaining membranes with high values of both
water permeability and water–salt selectivity, recent studies
emphasized the critical need for increased water–salt selectivity
rather than increased permeability for the design of TFC
membranes.11,12 Based on process modeling of the desalination
process, it was shown that further increments of water permeability
would have marginal influence on the energy efficiency of RO
systems. For example, in seawater desalination, a 5-fold increase of
water permeance of existing TFC membranes would only lead to
B3.7% reduction in energy consumption.11 Increasing water–salt
selectivity is important because RO exhibits relatively poor
rejection of small neutral molecules, such as boron and
disinfection byproducts, thus necessitating post-treatment
processes for their complete removal. These additional
processes, in turn, lead to increased capital and operating
costs, which could be avoided by using membranes with higher
water–salt selectivity. Thus, increasing the water–salt selectivity
of existing TFC membranes is a more effective strategy (the
green arrow in Fig. 4A) for improving system efficiency and
product water quality.
Water–solute selectivity of TFC membranes is determined by
the combined mechanisms of steric hindrance, Donnan exclusion,
and dielectric effect.13 Steric hindrance is related to the pore size
(or free volume) of polyamide, which allows molecules with
smaller sizes to permeate while keeping larger ones from doing
so. Donnan exclusion is governed by the fixed charge density on
the membrane surface. For example, a negatively charged surface
effectively rejects anions (e.g., Cl). To maintain electroneutrality
on both sides of the membranes, cations (e.g., Na+) are therefore
also excluded by the membrane, leading to a good overall rejection
of salts (e.g., NaCl). The dielectric effect is related to an energetic
penalty that solutes have to pay while transferring from a solvent
with a high dielectric constant (i.e., water) to a medium with a low
dielectric constant (i.e., polymer membrane material). The
presence of such an energetic penalty thus hampers the diffusion
of solutes (e.g., salt ions) through the membrane.
The three solute rejection mechanisms discussed above are
relevant to the material characteristics of the selective layer,
which stems from the molecular structure of the polyamide
materials. Taking crosslinking degree as an example, the
6294 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
polyamide forms a fully crosslinked structure (i.e., the ‘‘m’’
segment in Fig. 3) with a monomer ratio of 3 : 2 for MPD to
TMC. In an actual IP process, some linear segments (i.e., the
‘‘n’’ segment in Fig. 3) would also form under a monomer ratio
of 1 : 1 for MPD to TMC. In this case, unreacted acyl chloride
groups undergo hydrolysis to form carboxylic groups, thereby
imparting a negative charge to the membrane surface. The
crosslinked segments more rigidly resist swelling due to the
presence of chain linkages between polyamide backbones, thus
impeding solute transport. In contrast, the linear segments are
likely to undergo more severe swelling, which facilitates solute
transport within the polymer matrix. As shown in Fig. 4B, both
NaCl rejection and permselectivity exhibit an overall good
correlation with the crosslinking density, i.e., m/(m + n),
implying that increasing crosslinking segments is a feasible
strategy toward the design of membrane with high water–salt
selectivity. We note that this is only one example of how material
characteristics determine membrane transport properties. Efforts
to elucidate the structure–property–performance relationship of
the polyamide selective layer will be of paramount importance in
guiding the future design of high-performance TFC membranes.
2.2. Developing fouling-resistant membranes
Membrane materials effectively reject solutes to yield high-
quality product water. During operation, the rejected solutes
continuously accumulate on the membrane surface, leading to
membrane fouling. Fouling is widely considered the Achilles
heel for membrane processes as it leads to reduced process
performance. For instance, the presence of a foulant layer
increases the resistance for mass transport, resulting in a
continuous decrease in water flux. Periodic physical or
chemical cleaning is thus needed to mitigate fouling, leading
to frequent system shutdown and increased operating cost.
Therefore, understanding fouling mechanisms and developing
effective antifouling strategies are of critical importance.
Readers are referred to a recent comprehensive review to gain
more insights into membrane fouling.14
In seawater desalination, membrane fouling can be classified
into three categories (Fig. 4C): fouling by organic substances
(e.g., natural organic matter), scaling by inorganic species (e.g.,
gypsum or silica), and biologic fouling by microorganisms (e.g.,
bacteria or algae). The extent of fouling is governed by both
membrane surface properties and feedwater solution chemistry. The
surface properties of MPD-based TFC membranes—hydrophobic
nature, roughness, and presence of carboxylic groups—are
conducive to membrane fouling. Accordingly, surface modifi-
cations that render the membrane surface hydrophilic, smooth,
and of neutral charge, have been widely proposed as effective
antifouling strategies.15,16 In addition to surface modification,
fouling control could be achieved by adjusting solution
chemistry prior to membrane desalination. For example, a large
portion of organic and inorganic species could be removed in
pretreatment processes by adding coagulants or adjusting pH,
thereby reducing the overall fouling potential of the feedwater.3
Compared with other types of fouling, biofouling is even
more challenging, owing to the growth and proliferation of
This journal is © The Royal Society of Chemistry 2021

Tutorial Review
bacteria to form a sticky biofilm. Although the use of
disinfectants (e.g., chlorine) could effectively inactivate micro-
organisms, the chemical structure of polyamide is highly prone
to degradation when exposed to oxidants like chlorine.17,18
Polyamide degradation by chlorine undergoes a two-step
reaction—N-chlorination and ring chlorination—resulting in
irreversible damage to the polyamide selective layer and loss of
salt rejection properties.18 Therefore, complete removal of
chlorine in the feedwater is needed before membrane filtration.
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Notably, after membrane filtration, the product water is often
re-chlorinated for potable supply. Such complicated de- and
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
re-chlorination procedures decrease system efficiency remarkably,
thus necessitating the development of chlorine-resistant
membranes for biofouling control.17,18 Among the proposed
strategies are the use of oxidation-resistant monomers, incor-
poration of sacrificial materials, or surface modification.18,19
Despite these efforts, to date, there is no commercial chlorine-
resistant desalination membrane, highlighting the challenges
and the urgent need to develop such a membrane.
2.3. Understanding the reaction mechanisms of interfacial
polymerization
Membrane desalination is an interfacial separation process
where mass transport and fouling propensity are largely
governed by membrane surface characteristics. To date, most
surface characteristics (e.g., wettability, charge, and functional
groups) have been well investigated for their effects on
membrane performance. Researchers have also developed
numerous strategies to tune these characteristics for fabricating
high-performance membranes. In contrast, the origin of
membrane surface roughness resulting from the IP process
and its role in membrane performance are relatively poorly
understood.
The surface morphology of TFC membranes has a characteristic
ridge-and-valley structure, with polyamide protrusions of
B100 nm. Such rough structure may shield accumulated foulants
in the valley regions from being removed under the hydrodynamics
of crossflow filtration, thereby leading to increased membrane
fouling. In contrast, due to the presence of hollow cavities inside
the protrusions, the rough morphology also increases the
surface area for water transport, which is advantageous for TFC
membrane design. As such, attaining surface morphology that
could simultaneously inhibit fouling (low roughness) and facilitate
water transport (high roughness) is challenging.
Precise control of surface morphology relies on understanding
the formation mechanisms of the rough features during IP.
Two mechanisms have been proposed for the formation of the
ridge-and-valley structure during the IP process: interfacial
instability and formation of nano-size bubbles. For interfacial
instability, previous studies have suggested that the intense
exothermic reaction between TMC and MPD increases the local
temperature.20 Such temperature change at the interface
results in convective flow in the organic phase which forms
the rough features (Fig. 4D, upper region). For the second
mechanism—the formation of nanobubbles—studies suggest
that the increased local temperature, together with the
This journal is © The Royal Society of Chemistry 2021
View Article Online
Chem Soc Rev
generation of byproduct hydrochloric acid in the TMD–MPD
reaction, lead to the degassing of dissolved gas molecules (e.g.,
CO2, O2, and N2) in the aqueous phase (Fig. 4D, lower region).21
These bubbles are then encapsulated by the nascent polyamide
layer, leading to the formation of the ridge-and-valley structure.
However, only indirect evidence was obtained for supporting
these two mechanisms, thereby calling for more extensive
efforts to reveal the mechanisms of roughness formation.
3. Emerging strategies of interfacial
polymerization for fabricating TFC
membranes
Recent advances in thin-film fabrication processes and material
synthesis techniques enable innovative re-design of the IP
process. These newly proposed IP strategies aim to endow TFC
membranes with desired physicochemical characteristics,
thereby leading to performance gains in fouling resistance or
water–solute selectivity. Herein, we classify these emerging IP
strategies into four categories according to their underlying
design principles (Fig. 5) and discuss their respective advantages/
disadvantages for making high-performance TFC membranes.
Additionally, we compare the performance of membranes made
using these emerging strategies to state-of-the-art commercial
TFC membranes. Last, we discuss the key limitations of these
IP strategies and general trends in the future development of IP.
3.1. Constructing sacrificial interlayers on the support layer
IP reaction is performed on a microporous support membrane
that is formed by the non-solvent-induced phase separation
(NIPS) process. In brief, a film of polymer dissolved in solvent is
soaked in a non-solvent bath (e.g., water or ethanol). The
exchange of solvent and non-solvent leads to the precipitation
of the dissolved polymer into a solid thin film, thereby producing
a porous membrane structure.22 However, as NIPS is largely a
stochastic process, precise control over the structure of the
microporous support is relatively challenging, necessitating more
effective strategies for tuning characteristics of the support
prior to IP.
One strategy that attracts a growing interest is to construct a
sacrificial interlayer on the microporous support (Fig. 5A). The
sacrificial interlayers are generally made from nanomaterials
(e.g., nanostrands, nanotubes, or metal–organic frameworks)
with unique physicochemical properties (e.g., shape, wettability,
and charge), effectively modifying the support layer properties
before IP. For example, a layer of needle-like cadmium hydroxide
nanostrands was first deposited on a porous support.20 Using
the modified support for IP, the presence of this nanostrand
layer moved the interfacial reaction away from the solid support,
thereby resulting in a thin, smooth polyamide film.20 Although
this strategy was first demonstrated for membranes used in
organic solvent separation,20 similar techniques have recently
been applied for membranes for seawater desalination.23 Different
from the nanostrand layer, researchers deposited a composite
layer comprising a layer of carbon nanotubes (CNT) with a layer
Chem. Soc. Rev., 2021, 50, 6290–6307 | 6295
 View Article Online

Chem Soc Rev Tutorial Review

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

Fig. 5 Schematic diagrams of different types of emerging interfacial polymerization (IP) strategies for fabricating high-performance TFC membranes. (A)
Use of sacrificial interlayers for tuning support layer properties prior to IP. A sacrificial layer is first deposited on a substrate (upper panel). IP is performed
on the sacrificial-layer tailored substrate to form a polyamide layer on top (middle panel). The sacrificial layer is then removed by dissolving in a solvent
(lower panel). (B) Embedding of nanomaterials into the polyamide layer for obtaining a mixed-matrix structure. Nanofillers include nanoparticles,
nanotubes, nanosheets, and aquaporin vesicles, representing nanomaterials with 0D to 3D structures. (C) Tuning reaction conditions of IP by adding
different additives. In the upper left panel, the addition of polyvinyl alcohol (PVA) to the aqueous phase reduces the diffusion rate of PIP, leading to a
diffusion-driven instability and generating nanoscale spotted and striped Turing structures. In surfactant assembly regulated interfacial polymerization
(SARIP) (upper right panel), the addition of a surfactant, sodium dodecyl sulfate (SDS), results in a self-assembled network of amphiphiles at the water/
hexane interface, which facilitates the transport of PIP (red dots) across the interface to react with TMC (black dots). (D) Incorporation of new surface
coating techniques into IP processes. In electrospray process (upper panel), MPD (in aqueous phase) and TMC (in organic phase) solutions are
respectively introduced to two separate nozzles. A substrate stage is grounded and connected to the two nozzles with a direct current power source.
When high voltage is applied, the charged liquids leave the needles and emit microdroplets to deposit onto the substrate, where the reaction between
MPD and TMC leads to the formation of a thin polyamide film. In the molecular layer-by-layer process (lower panel), a substrate is alternately dipped into
the two monomer solutions (e.g., MPD in water and TMC in hexane) and subsequently rinsed with proper solvents (water and hexane) after each dipping
step. Such a dip-coating process is repeated for several cycles, resulting in a thin, defect-free film comprising multilayers of polyamide.

of zeolitic imidazolate framework (ZIF-8) on top.23 After the IP
reaction, the embedded ZIF-8 could be dissolved by immersing
the membrane in water, leading to the formation of a hollow
polyamide layer with crumpled surface structure. Such crumpled
structure resulted in an enhanced water permeability without
compromising salt rejection properties. Readers are referred to a
comprehensive review for the recent progress in the use of
sacrificial interlayers in IP.24
In addition to the use of nanomaterial-tailored supports,
another strategy is to perform IP at a free interface between an
aqueous phase and an organic phase.25,26 The liquid interface
enables more rapid heat dissipation than that in an aqueous
solution trapped in solid support, forming free-standing
nanofilms with smooth surfaces due to inhibition of interfacial
instability. The formed film could be used directly or
transferred to another porous support for performance

6296 | Chem. Soc. Rev., 2021, 50, 6290–6307 This journal is © The Royal Society of Chemistry 2021
 View Article Online

Tutorial Review Chem Soc Rev

evaluation. Such a strategy provides a useful platform for
isolating polyamide layers for advanced characterization in
order to unravel the structure–property–performance relationship
of the polyamide selective layer. However, as the polyamide layer
is relatively fragile with low mechanical strength, integrating such
free-standing films into membrane modules will be extremely
challenging. Moreover, even with an underlying support, the
interaction between the polyamide and the support will be much
weaker compared with that of conventional TFC membranes.
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
polyamide layer with favorable properties such as high water
permeance and biofouling resistance. These attempts have
introduced the concept of thin-film nanocomposite (TFN)
membranes; readers are referred to a comprehensive review to
learn more about TFN membranes.27 In the past decade, other
emerging materials with desired characteristics have also been
considered as embedded blocks in the polyamide layer. For
example, researchers prepared lipid vesicles laden with aquaporins,
which have unique water channels with high water permeability

Such low interaction would result in low resistance of the and salt selectivity.28,29 The presence of the aquaporin water
polyamide films to high-pressure or high-crossflow conditions, channels facilitated water transport through the polyamide layer
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

causing the films to lose their integrity during operation.
Therefore, further advances in material and process designs are
needed for expanding the real-world application of these free-
standing polyamide membranes.
3.2. Embedding nanofillers in the polyamide active layer
Embedding fillers in the polyamide selective layer is, potentially,
a direct strategy toward high-performance TFC membrane
fabrication (Fig. 5B); this strategy has been a topic of interest
for more than two decades.27 Following a typical IP process,
pre-synthesized fillers are added to the organic phase (mixed
with TMC) or aqueous phase (mixed with MPD), forming a mix-
matrix structure in the resulting polyamide layer. Early efforts
largely focused on the use of different nanofillers (e.g., nano-
particles, nanotubes, and nanosheets), which endowed the
while retaining ionic species, and readers are referred to a recent
comprehensive review.30
Despite the reported performance gain in water permeance
and fouling resistance through adding filler materials, real-
world applications of such composite membranes are still
hindered by several challenges, casting doubt about their
potential applicability. The most critical factor is the inevitable
formation of defects at the interface between fillers and the
polyamide matrix, which has been a long-standing issue for all
types of dense membranes with a mixed-matrix structure.31 The
formation of these defects is either ascribed to the low
miscibility between the two materials, or the inhibition of
the IP reaction to form less crosslinked polyamide regions.
For example, a recent study has observed the presence of
non-selective defect channels with a size of B2 nm between

Fig. 6 Characteristics and performance of TFC membranes fabricated through emerging interfacial polymerization (IP) strategies. (A) Effect of
embedded nanofillers on the mass transport of TFC membranes. Cross-section image of a polyamide layer with embedded silver nanoparticles (AgNP)
(left panel). The light-colored haloes around the silver nanoparticles correspond to lower mass density, suggesting the possible formation of
nanochannels with a size of 2–3 nm between a silver nanoparticle and the polyamide matrix (right panel). These channels potentially facilitate water
permeability while compromising water–solute selectivity. Scanning electron microscopy is adapted with permission from ref. 32, American Chemical
Society. (B) Schematic illustration of spatial distribution of water permeability sites with different polyamide morphologies, including spotted (left panel)
and stripped (right panel) Turing structures. Figure is reproduced with permission from ref. 39, American Association for the Advancement of Science. (C)
Schematic illustrations of a polyamide selective layer formed via conventional IP (left), which has a heterogeneous pore size distribution with the
presence of large pores, and surfactant-assembly regulated IP (SARIP) (right), which has a uniform pore size distribution. The uniform pore structure
endows the SARIP membranes with a precise solute–solute separation.

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 6290–6307 | 6297

Chem Soc Rev
embedded silver nanoparticles and polyamide matrix
(Fig. 6A),32 which are detrimental to membrane water–salt
selectivity. Although modifying fillers with hydrophobic
materials may enhance their miscibility in the polyamide
matrix and thus inhibit the formation of the defect
channels,33 the high liquid entry pressure (LEP) in these
hydrophobic nanopores would provide additional resistance
to water transport.34 For instance, a hydrophobic mesoporous
material (contact angle of 1401) with a pore diameter of 4 nm
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
requires an LEP of 138 bar, which is beyond the maximum
operating pressure in typical RO systems (i.e., B80 bar).
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
Notably, the use of the fillers in desalination membranes may
also result in the release of some filler materials to the product
water, leading to human exposure to these materials and
potential health impacts.1
3.3. Tuning reaction conditions of interfacial polymerization
Tuning reaction conditions of IP has been widely researched
since the origin of the TFC membranes. Previous efforts
through the control of monomer concentrations or adjustment
of curing conditions of IP have resulted in numerous commercial
products.8,35 New strategies involve the use of new reaction
monomers and additives in IP for making high-performance
TFC membranes.
Conventional IP is performed between a triacyl chloride
(particularly TMC) with a diamine—typically MPD for RO,
and piperazine (PIP) for NF. The reaction utilizes the high
reactivity between acyl chloride and amine groups, thereby
readily forming a dense selective layer at the organic–aqueous
solution interface. In essence, any pair of reactive chemicals,
which can be respectively dissolved in organic and aqueous
phases, could be potential monomers for IP. For example,
recent studies reported the use of hydroxyl-rich cyclodextrins
as alternative monomers of diamine to react with TMC.36 The
porous cyclodextrin molecules endow the formed nanofilms
with unique Janus pathways (i.e., hydrophobic inner cavities
and hydrophilic channels), thereby enabling precise molecular
sieving in both organic solvent separation and desalination.
Notably, recent efforts have expanded the search of alternative
monomers for IP to a broader range of chemicals as described
in these comprehensive reviews.37,38
Besides the use of new monomers, progress has also been
made in adding various additives to the IP reaction
(Fig. 5C).39,40 Different from new monomers, these additives
do not become segments of the resulting polyamide polymer.
Instead, they influence the formed polyamide selective layer by
inhibiting or facilitating the reaction between acyl chloride and
diamine at the interface. For example, in the conventional IP
process, the reaction predominantly occurs on the organic side
(i.e., TMC solution) of the interface, owing to the high diffusivity
of diamine monomers (e.g., MPD or PIP) from the aqueous
phase to the organic phase. Adding a macromolecule—polyvinyl
alcohol (PVA)—to the aqueous phase effectively inhibits the
diffusion of PIP, thus leading to a diffusion-driven Turing
instability at the interface (Fig. 5C, upper left panel).39 By
adjusting the amount of the PVA additive, the surface
6298 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
morphology of the polyamide layer could be manipulated to
form spotted (Fig. 6B, left panel) and striped (Fig. 6B, right
panel) Turing structures, thereby affecting the water transport in
the resulting membranes. In another study,40 an opposite strategy
was proposed to enhance the diffusion of PIP by adding surfactant
additives to the aqueous phase of diamine, leading to a new IP
process—surfactant assembly regulated interfacial polymerization
(SARIP) (Fig. 5C, upper right panel).40 It was suggested that
the trans-interface diffusion of PIP in the conventional IP is a
rate-limiting step, resulting in a heterogeneous polyamide
network (Fig. 6C, left panel) with a broad distribution of pore
sizes. Addition of sodium dodecyl sulfate (SDS) molecules to
the aqueous phase in SARIP leads to the formation of a
self-assembled dynamic network that facilitates the diffusion of
PIP across the interface. The increased amount of PIP in the TMC
solution results in a more homogeneous IP reaction, thus forming
a polyamide network with a more uniform pore size distribution
(Fig. 6C, right panel). Consequently, the SARIP membrane
exhibited a sharper cut-off for ion separation than the conven-
tional IP membrane, potentially enabling precise separation in
desalination and water purification.
3.4. Incorporating emerging surface coating techniques into
interfacial polymerization
The above-mentioned strategies involve the use of new chemicals
(e.g., nanostrands, nanofillers, monomers, or additives) for tailoring
the IP process. Presently, polyamide chemistry made from MPD
and TMC monomers remains the gold standard for commercial RO
membranes. This fact has driven innovations in the manufacturing
process of IP (Fig. 5D), while retaining the use of the conventional
MPD–TMC monomers—the pair that shows relevance and
potential to the industrial fabrication process.
As discussed above, the trans-interface diffusion of MPD
molecules is the major factor limiting the homogeneous
formation of a polyamide network. Additionally, the fast
kinetics of the MPD–TMC reaction lead to rapid formation of
a polyamide network, as the solution at the interface readily
reaches the gel point. This nascent polyamide gel provides
additional resistance for the diffusion of the two monomers
during the reaction. Consequently, the conventional IP process
produces selective polyamide layers with strong depth hetero-
geneity (i.e., variation in chemical structure from the surface to
the bottom) and rough surface morphology (i.e., characteristic
ridge-and-valley structure).41 To overcome these limitations,
molecular layer-by-layer (mLbL) deposition was proposed as
an alternative IP process (Fig. 5D, lower panel).42 In this
technique, a pretreated substrate is sequentially immersed in
MPD and TMC; the immersion is repeated for several cycles to
obtain an integral polyamide film. Notably, after each soaking,
the substrate is thoroughly rinsed to leave only a thin layer of
the reaction solution on the surface. In this case, the mLbL
technique builds the film with one molecular layer at a time via
instantaneous reaction of alternating MPD/TMC monomers,
thereby facilitating complete reaction between the monomers to
form an integral polyamide network. Compared with membranes
made through conventional IP, the mLbL-polyamide film not only
This journal is © The Royal Society of Chemistry 2021

Tutorial Review
has a smooth surface with enhanced fouling resistance, but
also exhibits increased NaCl rejection.42 Moreover, the mLbL
technique enables fine-tuning of reaction conditions (e.g., monomer/
solvent type, concentration, and support materials), as well as
nanoscale control of thickness, topology, and local chemical
composition of resulting polyamide films. Hence, the mLbL
technique holds promise as a versatile platform for revealing
the reaction mechanisms of IP.
Compared with the mLbL technique, more precise control of
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
reaction conditions could be achieved by integrating an electro-
spray technique—an ionization method developed for mass
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
spectroscopic analysis of polar biomolecules43—to the IP
process.44,45 In this process, MPD and TMC monomer solutions
are respectively loaded into two syringes (Fig. 5D, upper panel).
After applying a high voltage to the solution, the charged
solutions are ejected from the metallic needle and burst into
fine sprays due to the repulsive Coulombic forces. When both
MPD and TMC sprays deposit on a substrate, the polymeriza-
tion reaction takes place to form a polyamide layer. In essence,
the dropwise deposition of monomer solutions confines the
MPD–TMC reaction to the interface of the microdroplets,
leading to the formation of a smooth polyamide film.44,45 This
process enables nanoscale control of the film thickness
(B4 nm) through simple manipulation of reaction conditions,
such as monomer concentration,44 spraying time,45 or use of
different supports.44 Notably, the formed polyamide film exhibits
a thin layer (B10 nm) and good NaCl rejection (495%),44
demonstrating the promise of this emerging IP process in making
a thin, defect-free polyamide film for desalination.
3.5. Performance summary of TFC membranes made through
emerging techniques
As discussed earlier in this Tutorial, TFC membranes are
constrained by the permeability–selectivity trade-off (Fig. 7).
The intrinsic properties of commercial TFC membranes made
by conventional IP (blue squares) lay beneath an upper-bound
line. Such a trade-off relationship also holds true for TFC mem-
branes fabricated through emerging IP strategies (red circles).
Although the two groups of membranes exhibit comparable water
permeability values in the range of 1 to 5 L m2 h1 bar1, the
conventional-IP membranes substantially outperform the
emerging-IP membranes in water–salt selectivity. Such results
are not surprising, as the commercial membranes are the pro-
ducts obtained after a long-term optimization process. Presently,
emerging IP strategies are still at the stage of lab-scale research,
involving hand-cast procedures in making membranes. We expect
that some performance enhancement of the emerging-IP
membranes could be achieved by employing standard
manufacturing processes. However, the potential and feasibility
in scaling up these emerging IP strategies into real-world
industrial production processes should be carefully considered
and evaluated.
Notably, the low permselectivity of the emerging TFC
membranes was largely ascribed to the poor rejection of NaCl
salt. For instance, based on projected NaCl rejection,46 the area
beneath the upper bound line could be divided into several
This journal is © The Royal Society of Chemistry 2021
View Article Online
Chem Soc Rev
regions targeting different applications (Fig. 7, shaded areas).
The commercial membranes with excellent rejection of NaCl
largely lay in the seawater desalination RO region (SWRO, grey
area, RNaCl 4 99%), while the majority of the emerging TFC
membranes are in the brackish water RO region (BWRO, yellow
area, 99% 4 RNaCl 4 90%,) or nanofiltration region (NF, blue
area, RNaCl o 90%). As seawater is the dominant feedwater
source in the global share of desalination for water production
(460%),6 substantial efforts are needed to improve the water–
salt selectivity of the emerging TFC membranes, thereby
improving their performance for SWRO uses.
Notably, despite the performance gap between commercial and
emerging TFC membranes made of the polyamide chemistries,
the latter largely outperform membranes made of new emerging
materials, such as nanotubes and nanosheets (purple hexagons),
in terms of water–salt selectivity. While the discussion on
Fig. 7 Water permeability and water–salt selectivity of different types of
desalination membranes. The blue squares represent the performance of
commercial TFC membranes made through conventional IP. These
values are adapted from ref. 22. The red circles represent lab-made TFC
membranes fabricated via some emerging IP strategies reviewed in this
Tutorial. The transport properties of some emerging membrane materials
are also included in the figure for comparison (purple hexagons). The
green and orange dashed lines correspond to NaCl rejections of 99% and
90%, respectively, at a water flux of 20 L m2 h1. The area under the upper
bound line is further divided into three regions based on the threshold
NaCl rejection of 99% and 90%. Most commercial TFC membranes have
rejections in the seawater reverse osmosis (SWRO) region (rejection
4 99%), while the emerging TFC membranes have rejections in the
brackish water reverse osmosis (BWRO) region (90% o rejection o 99%)
and the nanofiltration (NF) rejection (rejection o 90%). The separation
performance of the conventional TFC membranes is relatively closer to the
upper bound line, owing to the well-developed and optimized systems for
the conventional IP. In contrast, the data points of the emerging TFC
membranes are far below the upper bound line, suggesting that substantial
efforts are needed to further optimize the fabrication conditions of the
emerging IP strategies.
Chem. Soc. Rev., 2021, 50, 6290–6307 | 6299

Chem Soc Rev
desalination membranes made from emerging materials via
non-IP methods is beyond the scope of this Tutorial, the low
performance of such membranes has been attributed to
defects inherent in the top-down fabrication methods used.22
Nevertheless, our analyses above demonstrate the promise of the
polyamide chemistries as well as the IP-based processes for
making high-performance desalination membranes.
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
4. Emerging techniques in
characterization of TFC membranes
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
Insights gained through in-depth characterization of TFC
membranes are important not only for understanding the
structure–property–performance relationship, but also for
future design and optimization of IP-based processes. Previous
efforts in probing TFC membrane structures largely relied on
the use of conventional tools, such as spectroscopy [e.g., X-ray
photoelectron spectroscopy (XPS) and Fourier-transform
infrared (FITR) spectroscopy] and microscopy [e.g., scanning
electron microscopy (SEM), transmission electron microscopy
(TEM), and atomic Force Microscope (AFM)] techniques.47
These tools have provided general structural information about
TFC membranes, like ridge-and-valley morphology, degree of
crosslinking, and functional group distribution of the
polyamide layer, facilitating the understanding of the TFC
membranes.
As discussed above, IP is a rapid self-inhibiting process that
enables the formation of a thin, defect-free polyamide film.
These features of IP, in turn, pose challenges for nanoscale
characterization of TFC membranes. For instance, when exploring
IP reaction mechanisms, the fast reaction kinetics between amine
and acyl chloride limit the direct observation of polyamide
network formation during the IP reaction using conventional
characterization tools. Moreover, the formed thin polyamide film
(B100 nm) only accounts for B1% of the total thickness of a
typical TFC membrane (B100 mm for the underlying polysulfone
support and PET fabric layers). When characterizing the
polyamide layer via conventional spectroscopic techniques, the
underlying support materials generate substantial amounts of
background noise that interferes with the characteristic
information of polyamide, hampering a closer look at the
polyamide layer alone. Consequently, along with the progress in
developing emerging IP strategies, recent years have also
witnessed substantial efforts in exploring new techniques for
TFC membrane characterization. These newly developed techniques
could be classified into two categories: direct imaging techniques
and indirect non-imaging techniques. An overview of these
techniques is presented below, and the pros and cons of each
technique are reviewed and discussed.
4.1. Direct imaging techniques
Direct imaging techniques aim to provide visual structural
information of the polyamide layer by using electron micro-
scopic tools (Fig. 8). In a regular cross-section TEM image
(Fig. 8a1), a characteristic ridge-and-valley structure could be
6300 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
observed on the top surface of TFC membranes. However,
discerning the polyamide–polysulfone interface (i.e., the
boundary between active and support layers) in such dark-
field images is difficult, because the polymeric materials with
dominant light elements (e.g., C, H, and O) on their backbones
are nearly ‘‘transparent’’ to electrons. Such a technological gap
necessitates effective measures to enhance the contrast
difference (Fig. 8A), thereby illustrating fine structures of the
polyamide layer and the polyamide–polysulfone interface.
One simple strategy is to stain the polyamide layer with
heavy metal elements (such as osmium, ruthenium, uranyl, and
lead).48–50 In a general procedure, TFC membranes are
immersed into a metal oxide solution, in which metal ions
readily approach and adhere to the charged regions of the
polyamide film. The stained membranes then undergo identical
sample preparation processes (i.e., fixation, dehydration, and
sectioning) and are imaged using electron microscopic techniques.
The metal stains absorb electrons or scatter part of the electron
beam which otherwise is projected onto the sample. As a result,
the stained polyamide layer is brighter than the unstained poly-
sulfone support in the dark-field images (Fig. 8a2). Previous studies
utilized such enhanced contrast to map the distribution of
functional groups in the polyamide layer.48,49 Recent
efforts—through tailoring staining conditions, together with
advances in a high-resolution electron microscope—have
enabled a closer look at the inner structure of the polyamide
layer.50 For example, precipitation of the metal stains on the outer
surface of the polyamide clearly illustrates the nodular shape of
the polyamide (Fig. 8a2). Moreover, the distribution of aqueous
stain tracers reflects actual transport pathways in the polyamide
layer, thereby revealing the ‘‘channel’’ structure for water transport
within the polyamide layer (inset of Fig. 8a2).50 Although such
‘‘channels’’ were also observed in non-stained samples (white
arrows in Fig. 8a1), staining substantially enhanced the contrast
for visualizing such fine structures.
Elemental mapping is another strategy for enhancing inter-
facial contrast.41 In particular, the polyamide active layer is rich
in nitrogen while the underlying polysulfone support layer
contains sulfur but no nitrogen. This intrinsic elemental contrast
allows researchers to perform an analysis using scanning
transmission electron microscopy (STEM) coupled with energy-
dispersive X-ray spectroscopy (EDX), for elucidating the nanoscale
structure and chemical composition.41 In the mapping image
(Fig. 8a3), fine structures at the polyamide–polysulfone interface
could be observed. For example, the presence of cavities inside the
ridge structure of both membranes (white arrows) suggests depth
heterogenicity of the polyamide film. Additionally, the polyamide
layer comprises a continuous 50 nm-thick polyamide base layer
(yellow arrow and bracket), from which the ridge-and-valley
structure extends outward.
Direct imaging of polyamide internal microstructure could
also be achieved through the isolation of the polyamide layer,
followed by 3D tomography visualization (Fig. 8B).51 In the
isolation step, the TFC membrane is immersed in a polar
solvent (e.g., DMF, NMP, and THF) to dissolve the underlying
polysulfone layer, while the structure of the insoluble
This journal is © The Royal Society of Chemistry 2021
 View Article Online

Tutorial Review Chem Soc Rev

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

Fig. 8 Direct imaging techniques for the characterization of TFC membranes. (A) Enhancement of interfacial contrast for the direct visualization of
polyamide–polysulfone interfacial structure. Comparison of scanning transmission electron microscopy (STEM) cross-section images of a non-stained
(a1) and a stained (a2) TFC membrane. Metal stains bound to the polyamide active layer result in convoluted regions (white arrowhead), enabling
differentiation of the interface and observation of the polyamide internal structure. The inset shows higher magnification of a region of polyamide layer
with empty (white arrow) and filled (yellow arrow) channels. Scanning electron microscopy images are adapted with permission from ref. 50, Elsevier. (a3)
Elemental mapping also presents a clear interfacial structure of a TFC membrane. This technique utilizes the elemental contrast between the polyamide
(abundant in nitrogen) and polysulfone (abundant in sulfur) layers. ‘‘N’’ (magenta) denotes nitrogen and ‘‘S’’ (green) denotes sulfur; the white arrows
indicate the cavities inside the ridge structure, while the yellow arrow and bracket indicate the dense polyamide layer. Scanning electron microscopy
image is adapted with permission from ref. 41, American Chemical Society. (B) Isolation of the polyamide layer for 3D tomographic characterization. (b1)
Schematic illustration of tomography techniques. A range of 2D images are collected using an advanced electron microscope by tilting the polyamide
film sample to many different angles. The 3D structure of the sample is then reconstructed from the images, thereby enabling further analysis of its
structural characteristics. (b2) 3D visualization of the spatial distribution of pore structure of various sizes within the interior of a polyamide film isolated
from a commercial TFC membrane. The pores are classified based on their respective internal sizes: singe voids have a size larger than 30 nm (green)
while the spheres have a size smaller than 30 nm (red) or 15 nm (yellow). Some single voids are connected to form some giant pores (blue). Figure is
adapted with permission from ref. 51, Elsevier. (b3) Tomographs of two commercial TFC membranes for SWRO and BWRO applications. The intensity of
the polyamide layers is displayed as a heat map, where red corresponds to higher intensity. Figure is adapted with permission from ref. 52, United States
National Academy of Sciences.

polyamide network is largely retained. The isolated polyamide
film is then imaged by TEM 3D tomography. By rotating the
sample around the tilt axis, a series of 2D projection images are
acquired at different tilt angles (normally within a range of
791 to +791). After alignment and processing, the tilt series are
reconstructed into a 3D model of the isolated polyamide film,
thereby providing information on its internal structure.51 For
example, in a tomogram of a commercial TFC membrane
(Fig. 8b2), internal voids with various sizes and shapes were
clearly illustrated.51 These voids, which govern the pathways of
flow and diffusion across the polyamide layer, were either
connected to the outside of the polyamide film or
encapsulated within the polyamide matrix.
Following the progress in TEM tomography, scanning TEM
(STEM) has also been introduced for imaging polyamide layers
(Fig. 8b1).52,53 Unlike the use of a parallel, coherent beam of
electrons for imaging in conventional TEM, STEM technique
scans a focused beam of electrons across a sample. Such
dynamic focus effectively reduces the defocus variation in
TEM imaging of a thick sample at a high-tilt angle,52 thereby
providing high-quality images of soft materials for nanoscale
analysis. Moreover, STEM tomography operated in high-angle
annular dark-field (HAADF) mode can provide additional
information about polymeric structures, such as mass,
thickness, and atomic number.52,53 For instance, in heat
maps of the STEM images of two commercial TFC
membranes (Fig. 8b3), the membrane for seawater RO
(SWRO, upper panel) exhibits a much denser structure (red
area) than that of the membrane for brackish water RO (BWRO,
lower panel).52 The denser structure is likely the actual selective
barrier of polyamide, which is responsible for the higher salt
rejection and lower water permeance of the SWRO membrane
compared to the BWRO.52,53
4.2. Indirect non-imaging techniques
Parallel to efforts in direct imaging techniques, progress has
also been made in using non-imaging techniques for TFC
membrane characterization. These techniques, coupled with
spectroscopic or scattering tools, shed light on chemical
composition, nanopore size distribution, and polymeric chain

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 6290–6307 | 6301

Chem Soc Rev
structure within the polyamide layer, thereby providing
additional valuable information for revealing the membrane’s
internal structure.
As discussed earlier, conventional spectroscopic methods
provide limited information about the polyamide internal
structure. Researchers sought to develop effective characterization
strategies to fully explore the capability of the spectroscopic
techniques. An earlier example was impregnating the polyamide
layer with silver nitrate solution, in which silver ions selectively
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
bind to negatively charged carboxyl groups at a 1 : 1 ratio.54
The impregnated polyamide is then characterized by Rutherford
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
backscattering spectrometry (RBS), which detects the amount of
the bound silver probe for determining the volume density of
carboxyl groups. Using this technique, other useful information,
such as ionization behaviors and ion accessibility, could also be
revealed by adjusting characterization conditions (e.g., impregnation
pH or ion probe types).54 However, this silver-RBS method has not
been widely used in membrane characterization, largely owing to
the inaccessibility of the specialized RBS instrument. In a later
effort,55 researchers modified the silver-binding procedure used in
RBS by including a low-pH elution step, which allowed the use of a
more accessible spectroscopic technique—inductively coupled
plasma mass spectrometry—to quantify the eluted silver concen-
tration for determining carboxyl density of the polyamide layer.
In addition to the volume density of functional groups,
spectroscopic techniques could also be combined with incident
high beams for revealing the depth profile of the polyamide
layer.41,56 For example, XPS—a technique that only probes the
very top surface of the polyamide layer (o5 nm)—could be
paired with C60+ cluster ion sputtering platform.41 In this
combined technique, the polyamide side of TFC membranes
is exposed to a high beam generated from C60+ bombardment,
enabling controllable sputtering of the polyamide layer. At
different sputtering times, XPS elemental scans are performed
on the sputtered spot in order to reveal the atomic composition
and chemical state of the organic thin films with depth.41 In a
similar technique called elastic recoil detection (ERD), a
membrane sample is bombarded with a high-energy iodine
beam, causing target atoms (e.g., C, N, O, S, and Cl) to be
scattered out of the sample.56 Analysis of the scattered signal
not only identifies the recoil ion species according to their
respective nuclear charge or mass, but also detects the energy
of the recoil ions.56 This latter information is then used to
determine the energy loss between the projectile and the recoil
ion within the sample matrix, thereby enabling analysis of
elemental depth profiling of the membrane sample. Notably,
the depth profiles extracted from these spectroscopic tools (i.e.,
XPS-C60+ and ERD) revealed the presence of a heterogeneous
layer that contains both polyamide and polysulfone
signatures.41,56 Such a structure implies that the polyamide
penetrates the pores of polysulfone during IP reaction, anchoring
to the support to form a stable TFC structure.
Positron annihilation lifetime spectroscopy (PALS) is
another technique capable of probing the internal pore structure
of the polyamide layer on TFC membranes.57 The analysis is
conducted by injecting low-energy positrons into the polyamide
6302 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
layer, where each positron combines with an electron to form an
electron–positronium (Ps) ion. These Ps ions tend to locate in
electron-deficient regions, such as free volume and pores, and
undergo a slow self-annihilation process with a long lifetime. In
electron-rich regions that were occupied by the polyamide
matrix, the Ps ions would interact with surrounding molecularly
bound electrons to induce a rapid annihilation process with
a short lifetime. By correlating the lifetime of the injected
positrons with the sample void size, PALS could reveal charac-
teristics of pore structure, such as size, distribution, and film
thickness. For example, using this technique, researchers were
able to reveal the presence of two types of pores within the
polyamide layer of an RO membrane, i.e., smaller intrachain
network pores (B0.45 nm) and larger interchain aggregate pores
(B0.8 nm).57 This sub-nanometer insight has enabled substantial
progress in elucidating the structure–performance relationship of
TFC membranes, as well as in understanding the reaction
mechanisms on IP. Readers are referred to a recent comprehensive
review for a detailed introduction of PALS in membrane
characterization.58
Besides advances in spectroscopic techniques, recent years
have also witnessed increasing interest in using scattering
techniques for TFC membrane characterization (Fig. 9).59–61
During the measurements, the incident sources (e.g., X-ray or
neutron) are scattered by the electrons (X-ray) or the nuclei
(neutron) to generate corresponding signals (Fig. 9A). Generally,
the interference of scattered sources from neighboring planes
could be described by Bragg’s law: nl = 2d sin y, where y is the
scattering angle, d is the distance between the atomic planes
(d-spacing), l is the wavelength of the incident source, and n is
an integer. As the scattering vector, q, is related to y by the
relation q = 4p sin y/l, Bragg’s law could be written as d = 2p/q. In
principle, Bragg’s law is applicable to crystalline materials with
repeating discrete reflections. However, the inverse relationship
of the actual length scale, d, and the reciprocal space, q, could
still be used in the interpretation of the interchain distance in
amorphous materials, such as highly crosslinked polyamide. For
example, wide-angle X-ray scattering (WAXS) generally collects
scattered signals with q 4 0.5 Å1, corresponding to the atomic
or molecular structures with d = 0.1–10 Å, while small-angle X-ray
scattering (SAXS) or small-angle neutron scattering (SANS)
collect scattered signals with q range of 0.005–0.5 Å1 for
revealing mesoscale structure (i.e., d = 10–1000 Å) from the
aggregates or clusters of atoms and molecules.
Two types of polyamide samples are commonly used in
scattering experiments: polyamide film and bulk dispersion.
In film characterization mode (Fig. 9B), incident X-ray is shed
on a polyamide film at a relatively small angle, and scattered
signals are then detected by a 2D detector.59 As the film is
horizontally positioned on a sample stage, analysis of scattering
patterns could provide information on both molecular structure
and preferential orientation (either in-plane or out-of-plane) of
the polyamide network.59 For example, an arc-like meridional
scattering feature in a WAXS pattern (Fig. 9C), where intense
scattering is preferentially aligned along the vertical qz direction,
implies the in-plane orientation of aromatic stacking in the
This journal is © The Royal Society of Chemistry 2021
 View Article Online

Tutorial Review Chem Soc Rev

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.

Fig. 9 Indirect scattering techniques for the characterization of TFC membranes. (A) Interaction of atomic matter with scattering sources to generate
scattering signals. X-rays interact with electrons in the material via an electromagnetic force, while neutrons interact with the nucleus via the very short-
range strong nuclear force. (B) Schematic illustration of the experimental setup used for characterizing a polyamide film using wide-angle X-ray
scattering (WAXS). A representative anisotropic pattern on a 2D WAXS detector provides information on the molecular structure and preferential
orientations in the polyamide film. (C) A representative WAXS pattern of a polyamide film. The horizontal (qr) and vertical (qz) vectors correspond to the
surface parallel and normal scattering wave vectors, respectively. Dashed arcs are scattering vectors of 1.22, 1.54, and 1.79 Å1, corresponding to the
spacing of 5.2, 4.1, and 3.5 Å, respectively. Figure is adapted with permission from ref. 59, American Chemical Society. (D) Different stacking behaviors of
aromatic rings within a polyamide layer. The green dashed lines indicate the distance of 3.5 Å for the aromatic cores stacked in p–p (parallel) structure,
while the red dash lines indicate the distance of 5.2 Å for the aromatic cores stacked in T-shaped (orthogonal) structure. (E) Schematic illustration of
small-angle X-ray scattering (SAXS) platform used for characterizing polyamide bulk dispersion. Solid polyamide film is ground into small flakes and
dispersed in water as a colloidal-like suspension, thus resulting in a pattern of isotropic rings on a 2D SAXS detector. (F) Schematic diagram of 1D
scattering intensity profile of polyamide by integrating a 2D SAXS pattern. The profile can be divided into three regions for respective analysis. In the
Guinier region, scattering intensity, I, is proportional to the concentration of the system and thus independent of q. In the mass fractal (I p q2–3) and the
Porod region (I p q3–4), the correlation of I with q can provide the structural information of large clusters and small primary units of polyamide chain,
respectively.

polyamide film.59 Further analysis of this WAXS pattern by
plotting the scattered intensity versus scattering vector, q,
suggests the presence of two peaks centered at 1.79 Å1 and
1.22 Å1. According to Bragg’s law (d = 2p/q), these two peaks
correspond to molecular spacings of 3.5 and 5.2 Å, respectively.
The 3.5 Å spacing is consistent with ‘‘p–p’’ stacking of aromatic
cores (green arrows in Fig. 9D), whereas the 5.2 Å spacing is
consistent with the perpendicular packing of aromatic cores in
the ‘‘T-shaped’’ configuration (red arrows in Fig. 9D).59 Based on
such WAXS results, researchers revealed the important role of
reaction kinetics and post-treatment procedures in affecting the
stacking behaviors of aromatic rings. For example, the emerging
mLbL IP strategy with well-controlled MPD–TMC reaction
leads to the generation of parallel ‘‘p–p’’ stacking, while the
conventional IP processes with uncontrolled MPD–TMC reaction
give rise to ‘‘T-shaped’’ configurations. It is surmised that the
‘‘T-shaped’’ stacking with loose structure is more favorable for
water diffusion, thereby governing the mass transport of
polyamide films.
Besides the molecular-level insights from the WAXS
measurement of polyamide films, SAXS (or SANS) measurements
were used to characterize polyamide dispersions for revealing
structural information at the polymer-chain level (Fig. 9E).60,61
Prior to the scattering experiments, freshly-prepared polyamide
films are either loaded into a small quartz capillary,61 or ground
into small flakes and dispersed in water as a colloidal-like
suspension.60 Integration of 2D scattering pattern results in a
1D scattering profile (schematic illustrated in Fig. 9F), which
could be divided into three regions for respective analysis.61
In the Guinier region (extremely low q), scattering intensity, I,
is proportional to the concentration of the system and thus
independent of q. At a higher q, the correlation of I with q could
provide information on polyamide chain structure, including
larger clusters or smaller primary units. For example, in the
Porod region (I p q3–4), the SAXS pattern of an RO polyamide
layer reveals that the primary globular units have a radius of
B130 Å, containing B1500 phenylenediamine trimesamide
units.61 In comparison, the primary unit of an NF polypiperazine
layer is slightly smaller, having radii of B120 Å with B1400
piperazine trimesamide units.61 Additionally, a steeper slope for
the NF membranes (log I/log q = 3.8) than that for the RO
membranes (log I/log q = 3.4) suggests that the globular units
in the NF membranes have a relatively higher degree of
compaction than those in the RO membranes.61 Notably, the
aggregation of these primary units leads to the formation of
larger clusters, which could also be characterized by the SAXS

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev., 2021, 50, 6290–6307 | 6303

Chem Soc Rev
profiles in the mass fractal regions (I p q2–3). For instance, the
nodular clusters of the NF polypiperazine network have a size of
1900–3000 Å, which is six times larger than that of the RO
polyamide network. Taken together, these insights from the
scattering studies suggest that the RO polyamide layer has larger
primary units, lower chain compaction, and smaller size
clusters than those of the NF polypiperazine layer.60,61 Such
differences in the polymer network structures could be related
to their desalination performance, thereby facilitating the
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
understanding of the IP reaction for guiding the design of
high-performance TFC membranes.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
5. Conclusion and outlook
In this Tutorial, we presented a brief history of the development
of desalination membranes, discussed the current challenges
in the application of conventional TFC membranes, and
reviewed emerging progress in IP-based fabrication processes
and TFC membrane characterization techniques. Despite
extensive research efforts in the past decade, the industrial IP
process and its product polyamide layer are largely unchanged
since the invention of TFC membranes in the late 1970s,
suggesting knowledge gaps between lab research and real-world
applications. Herein, we further discuss key limiting factors of the
IP process and propose potential research directions for fabricating
next-generation TFC desalination membranes.
Development of new IP strategies has been an active area of
research in the past decade, as reviewed in this Tutorial.
Presently, obtaining a polyamide layer with a smooth surface
for fouling control is possible using some emerging
approaches, such as electrospray or constructing sacrificial
interlayers. However, effective strategies for making membranes
with ultrahigh water–salt selectivity are still lacking, mainly
owing to the challenges in obtaining a thin, defect-free poly-
amide film after adjusting reaction conditions of IP. Given the
importance of enhanced water–salt selectivity in improving
water quality and reducing the cost of desalination, future efforts
in developing new IP strategies would require effective measures
of molecular-level manipulation of polyamide microstructures
where water and solute transport takes place. For example,
controlling reaction or posttreatment conditions of IP resulted
in different molecular motifs of polyamide, potentially affecting
mass transport in TFC membranes.59 Such insights may lead to
new approaches for making high-performance membranes.
Notably, advances in materials science related to thin-film
fabrication techniques (e.g., self-assembly,62 atomic layer
deposition,63 and surface-initiated polymerization64) can provide
new approaches for the design of novel IP strategies.
The use of advanced characterization techniques has
enabled substantial progress in the mechanistic understanding
of the IP reaction and membrane structure. However, techniques
for in situ characterization of IP reaction kinetics, as well as
operando characterization of TFC membranes, are still lacking.
As discussed in this Tutorial, the fast kinetics of the IP reaction
limit direct observation of polyamide formation. Moreover, the
6304 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
IP reaction involves the generation of heterogeneous
environments with both liquid solution and solid polyamide,
adding further constraints to the system for in situ characteriza-
tion. For the resulting membranes, existing characterization is
largely conducted under ambient conditions, while operando
characterization of TFC membranes under conditions relevant
to real-world operation (e.g., high pressure, crossflow, and
salinity) is hampered by numerous technical obstacles. For
instance, electron microscopic tools require stringent sample
pretreatment (e.g., drying, sectioning, or coating), thereby
limiting their uses for operando characterization. Although
X-ray (or neutron) scattering techniques do not require sample
pretreatment, incorporating custom-built setups, which can
mimic the operating conditions, into existing facilities is extremely
difficult. Given the importance of in situ or operando information
in delineating reaction mechanisms of IP and structure–property–
performance relationship of TFC membranes, increasing efforts
should be devoted to developing relevant characterization tools
and platforms in future research.
In addition to the efforts in developing experimental measures
with the required spatial and temporal resolution, molecular
simulations can be a versatile tool to gain insights into the IP
reaction kinetics and polyamide formation mechanisms. For
example, a recent study using molecular dynamic simulation
predicted the presence of ‘‘p–p’’ and ‘‘T-shaped’’ stacking for
the aromatic rings of the polyamide structure,65 thereby guiding
the selection and design of pertinent characterization tools in
revealing such microstructures (see the above section about X-ray
scattering techniques).59 In another simulation study, researchers
suggested a reaction-aggregation process of IP in forming small
polyamide oligomers, which then aggregated to yield large, solid
polyamide clusters to limit further reaction of IP.66 Notably, their
modeling results were also validated by an experimental study,67
demonstrating the promise of the developed model in studying
the complex IP reaction kinetics. Despite such progress, current
efforts in the simulation of IP are still in their infancy, largely
relying on molecular dynamic simulations.65,66,68 With recent
advances in computation, molecular simulations can play more
important roles in understanding IP reaction mechanisms and
guiding TFC membrane design. For instance, the utilization of
supercomputers can enable more complicated simulations of the
IP reaction by taking more reaction factors into consideration.
The development of machine learning or artificial intelligence can
also relieve researchers of some tedious, time-consuming experi-
ments in finding the best reaction conditions.
Last, in addition to research efforts in academia, the design
of IP processes for making next-generation TFC membranes
would also require collaborative efforts with the industry. After
long-term optimization of the conventional IP process,
membrane industries have established an inventory of
empirical protocols to making high-performance TFC
membranes for different applications, including seawater
desalination, wastewater reclamation, or even tap water
softening. However, owing to the lack of interactions between
academia and industry, a large portion of research efforts in
academia still focus on tuning minor conditions of IP to
This journal is © The Royal Society of Chemistry 2021

Tutorial Review
achieve marginal gains in membrane performance, which may
have been realized by industry a long time ago. To avoid such
superficial repetition in future research, academic researchers
should put more emphasis on revealing IP reaction mechanisms
or demonstrating proof-of-concept of new IP strategies, while
seeking collaborations with industrial partners in scaling up lab
results into commercial products. Such collaborative experiences
will enable academic researchers to understand not only the
design factors for high-performance membranes, but also the
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
factors that afford scalable production processes.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We acknowledge the financial support received from the NSF
Nanosystems Engineering Research Center for Nanotechnology-
Enabled Water Treatment (EEC-1449500). This work was partly
supported by the Fundamental Research Funds for the Central
Universities. We also acknowledge fruitful discussions with Wen
Ma, Jay Werber, Akshay Deshmukh, and Rhea Verbeke at Yale
University.
References
1 M. S. Mauter, I. Zucker, F. Perreault, J. R. Werber, J.-H. Kim
and M. Elimelech, The role of nanotechnology in tackling
global water challenges, Nat. Sustain., 2018, 1, 166–175.
2 M. A. Shannon, P. W. Bohn, M. Elimelech, J. G. Georgiadis,
B. J. Marinas and A. M. Mayes, Science and technology for
water purification in the coming decades, Nature, 2008, 452,
301–310.
3 M. Elimelech and W. A. Phillip, The Future of Seawater
Desalination: Energy, Technology, and the Environment,
Science, 2011, 333, 712–717.
4 R. Weaver, M. Howells, Y. Yang, S. Lennox and H. Brown,
IDA Water Security Handbook 2019–2020, 2020.
5 A. Deshmukh, C. Boo, V. Karanikola, S. Lin, A. P. Straub,
T. Tong, D. M. Warsinger and M. Elimelech, Membrane
distillation at the water-energy nexus: limits, opportunities,
and challenges, Energy Environ. Sci., 2018, 11, 1177–1196.
6 E. Jones, M. Qadir, M. T. H. van Vliet, V. Smakhtin and
S.-M. Kang, The state of desalination and brine production:
A global outlook, Sci. Total Environ., 2019, 657, 1343–1356.
7 J. Glater, The early history of reverse osmosis membrane
development, Desalination, 1998, 117, 297–309.
8 R. W. Baker, Membrane Technology and Applications, Wiley,
New York, 2nd edn, 2004.
9 G. M. Geise, H. B. Park, A. C. Sagle, B. D. Freeman and
J. E. McGrath, Water permeability and water/salt selectivity
tradeoff in polymers for desalination, J. Membr. Sci., 2011,
369, 130–138.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Chem Soc Rev
10 H. B. Park, J. Kamcev, L. M. Robeson, M. Elimelech and
B. D. Freeman, Maximizing the right stuff: The trade-off
between membrane permeability and selectivity, Science,
2017, 356, eaab0530.
11 J. R. Werber, A. Deshmukh and M. Elimelech, The Critical
Need for Increased Selectivity, Not Increased Water Perme-
ability, for Desalination Membranes, Environ. Sci. Technol.
Lett., 2016, 3, 112–120.
12 D. Cohen-Tanugi, R. K. McGovern, S. H. Dave, J. H. Lienhard
and J. C. Grossman, Quantifying the potential of ultra-
permeable membranes for water desalination, Energy
Environ. Sci., 2014, 7, 1134–1141.
13 X. Zhou, Z. Wang, R. Epsztein, C. Zhan, W. Li, J. D. Fortner,
T. A. Pham, J.-H. Kim and M. Elimelech, Intrapore energy
barriers govern ion transport and selectivity of desalination
membranes, Sci. Adv., 2020, 6, eabd9045.
14 R. Zhang, Y. Liu, M. He, Y. Su, X. Zhao, M. Elimelech and
Z. Jiang, Antifouling membranes for sustainable water
purification: strategies and mechanisms, Chem. Soc. Rev.,
2016, 45, 5888–5924.
15 D. Rana and T. Matsuura, Surface Modifications for Anti-
fouling Membranes, Chem. Rev., 2010, 110, 2448–2471.
16 G.-D. Kang and Y.-M. Cao, Development of antifouling
reverse osmosis membranes for water treatment: A review,
Water Res., 2012, 46, 584–600.
17 J. Glater, S. K. Hong and M. Elimelech, The Search for a
Chlorine-Resistant Reverse-Osmosis Membrane, Desalina-
tion, 1994, 95, 325–345.
18 R. Verbeke, V. Gómez and I. F. J. Vankelecom, Chlorine-
resistance of reverse osmosis (RO) polyamide membranes,
Prog. Polym. Sci., 2017, 72, 1–15.
19 Y. Yao, P. Zhang, C. Jiang, R. M. DuChanois, X. Zhang and
M. Elimelech, High performance polyester reverse osmosis
desalination membrane with chlorine resistance, Nat. Sus-
tain., 2021, 4, 138–146.
20 S. Karan, Z. Jiang and A. G. Livingston, Sub–10 nm
polyamide nanofilms with ultrafast solvent transport for
molecular separation, Science, 2015, 348, 1347–1351.
21 X.-H. Ma, Z.-K. Yao, Z. Yang, H. Guo, Z.-L. Xu, C. Y. Tang and
M. Elimelech, Nanofoaming of Polyamide Desalination
Membranes To Tune Permeability and Selectivity, Environ.
Sci. Technol. Lett., 2018, 5, 123–130.
22 J. R. Werber, C. O. Osuji and M. Elimelech, Materials for
next-generation desalination and water purification
membranes, Nat. Rev. Mater., 2016, 1, 16018.
23 Z. Wang, Z. Wang, S. Lin, H. Jin, S. Gao, Y. Zhu and J. Jin,
Nanoparticle-templated nanofiltration membranes for
ultrahigh performance desalination, Nat. Commun., 2018,
9, 2004.
24 Z. Yang, P.-F. Sun, X. Li, B. Gan, L. Wang, X. Song, H.-D.
Park and C. Y. Tang, A Critical Review on Thin-Film
Nanocomposite Membranes with Interlayered Structure:
Mechanisms, Recent Developments, and Environmental
Applications, Environ. Sci. Technol., 2020, 54, 15563–15583.
25 S.-J. Park, W. Choi, S.-E. Nam, S. Hong, J. S. Lee and J.-H.
Lee, Fabrication of polyamide thin film composite reverse
Chem. Soc. Rev., 2021, 50, 6290–6307 | 6305

Chem Soc Rev
osmosis membranes via support-free interfacial polymeriza-
tion, J. Membr. Sci., 2017, 526, 52–59.
26 Z. Jiang, S. Karan and A. G. Livingston, Water Transport
through Ultrathin Polyamide Nanofilms Used for Reverse
Osmosis, Adv. Mater., 2018, 30, 1705973.
27 M. M. Pendergast and E. M. V. Hoek, A review of water
treatment membrane nanotechnologies, Energy Environ.
Sci., 2011, 4, 1946–1971.
28 Y. Zhao, C. Qiu, X. Li, A. Vararattanavech, W. Shen, J. Torres,
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
C. Hélix-Nielsen, R. Wang, X. Hu, A. G. Fane and C. Y. Tang,
Synthesis of robust and high-performance aquaporin-based
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
biomimetic membranes by interfacial polymerization-
membrane preparation and RO performance characteriza-
tion, J. Membr. Sci., 2012, 423-424, 422–428.
29 X. Li, S. Chou, R. Wang, L. Shi, W. Fang, G. Chaitra,
C. Y. Tang, J. Torres, X. Hu and A. G. Fane, Nature gives
the best solution for desalination: Aquaporin-based hollow
fiber composite membrane with superior performance,
J. Membr. Sci., 2015, 494, 68–77.
30 C. J. Porter, J. R. Werber, M. Zhong, C. J. Wilson and
M. Elimelech, Pathways and Challenges for Biomimetic
Desalination Membranes with Sub-Nanometer Channels,
ACS Nano, 2020, 14, 10894–10916.
31 E. M. V. Hoek and V. V. Tarabara, Encyclopedia of membrane
science and technology, Wiley Online Library, 2013.
32 Z. Yang, H. Guo, Z.-K. Yao, Y. Mei and C. Y. Tang, Hydro-
philic Silver Nanoparticles Induce Selective Nanochannels
in Thin Film Nanocomposite Polyamide Membranes,
Environ. Sci. Technol., 2019, 53, 5301–5308.
33 J. Yin, Z. Yang, C. Y. Tang and B. Deng, Probing the
Contributions of Interior and Exterior Channels of
Nanofillers toward the Enhanced Separation Performance
of a Thin-Film Nanocomposite Reverse Osmosis Membrane,
Environ. Sci. Technol. Lett., 2020, 7, 766–772.
34 M. Mulder, Basic Principles of Membrane Technology, Kluwer
Academic Pulisher, The Netherlands, 2nd edn, 1996.
35 R. J. Petersen, Composite Reverse-Osmosis and Nanofiltra-
tion Membranes, J. Membr. Sci., 1993, 83, 81–150.
36 J. Liu, D. Hua, Y. Zhang, S. Japip and T.-S. Chung, Precise
Molecular Sieving Architectures with Janus Pathways for
Both Polar and Nonpolar Molecules, Adv. Mater., 2018,
30, 1705933.
37 M. J. T. Raaijmakers and N. E. Benes, Current trends in
interfacial polymerization chemistry, Prog. Polym. Sci., 2016,
63, 86–142.
38 A. F. Ismail, M. Padaki, N. Hilal, T. Matsuura and W. J. Lau,
Thin film composite membrane—Recent development and
future potential, Desalination, 2015, 356, 140–148.
39 Z. Tan, S. Chen, X. Peng, L. Zhang and C. Gao, Polyamide
membranes with nanoscale Turing structures for water
purification, Science, 2018, 360, 518–521.
40 Y. Liang, Y. Zhu, C. Liu, K.-R. Lee, W.-S. Hung, Z. Wang,
Y. Li, M. Elimelech, J. Jin and S. Lin, Polyamide nanofiltra-
tion membrane with highly uniform sub-nanometre pores
for sub-1 Å precision separation, Nat. Commun., 2020,
11, 2015.
6306 | Chem. Soc. Rev., 2021, 50, 6290–6307
View Article Online
Tutorial Review
41 X. Lu, S. Nejati, Y. Choo, C. O. Osuji, J. Ma and
M. Elimelech, Elements Provide a Clue: Nanoscale Charac-
terization of Thin-Film Composite Polyamide Membranes,
ACS Appl. Mater. Interfaces, 2015, 7, 16917–16922.
42 G. Joung-Eun, L. Seunghye, C. M. Stafford, L. J. Suk,
C. Wansuk, K. Bo-Young, B. Kyung-Youl, E. P. Chan,
C. J. Young, B. Joona and L. Jung-Hyun, Molecular
Layer-by-Layer Assembled Thin-Film Composite Mem-
branes for Water Desalination, Adv. Mater., 2013, 25,
4778–4782.
43 J. Fenn, M. Mann, C. Meng, S. Wong and C. Whitehouse,
Electrospray ionization for mass spectrometry of large bio-
molecules, Science, 1989, 246, 64–71.
44 M. R. Chowdhury, J. Steffes, B. D. Huey and
J. R. McCutcheon, 3D printed polyamide membranes for
desalination, Science, 2018, 361, 682–686.
45 X.-H. Ma, Z. Yang, Z.-K. Yao, H. Guo, Z.-L. Xu and C. Y. Tang,
Interfacial Polymerization with Electrosprayed Microdro-
plets: Toward Controllable and Ultrathin Polyamide Mem-
branes, Environ. Sci. Technol. Lett., 2018, 5, 117–122.
46 Z. Yang, H. Guo and C. Y. Tang, The upper bound of thin-
film composite (TFC) polyamide membranes for desalina-
tion, J. Membr. Sci., 2019, 590, 117297.
47 P. S. Singh, A. P. Rao, P. Ray, A. Bhattacharya, K. Singh,
N. K. Saha and A. V. R. Reddy, Techniques for characteriza-
tion of polyamide thin film composite membranes, Desali-
nation, 2011, 282, 78–86.
48 V. Freger, A. Bottino, G. Capannelli, M. Perry, V. Gitis and
S. Belfer, Characterization of novel acid-stable NF mem-
branes before and after exposure to acid using ATR-FTIR,
TEM and AFM, J. Membr. Sci., 2005, 256, 134–142.
49 C. Y. Tang, Y.-N. Kwon and J. O. Leckie, Probing the nano-
and micro-scales of reverse osmosis membranes—A com-
prehensive characterization of physiochemical properties of
uncoated and coated membranes by XPS, TEM, ATR-FTIR,
and streaming potential measurements, J. Membr. Sci.,
2007, 287, 146–156.
50 M. M. Kłosowski, C. M. McGilvery, Y. Li, P. Abellan,
Q. Ramasse, J. T. Cabral, A. G. Livingston and A. E. Porter,
Micro-to nano-scale characterisation of polyamide struc-
tures of the SW30HR RO membrane using advanced elec-
tron microscopy and stain tracers, J. Membr. Sci., 2016, 520,
465–476.
51 F. Pacheco, R. Sougrat, M. Reinhard, J. O. Leckie and
I. Pinnau, 3D visualization of the internal nanostructure
of polyamide thin films in RO membranes, J. Membr. Sci.,
2016, 501, 33–44.
52 T. E. Culp, Y.-X. Shen, M. Geitner, M. Paul, A. Roy,
M. J. Behr, S. Rosenberg, J. Gu, M. Kumar and
E. D. Gomez, Electron tomography reveals details of the
internal microstructure of desalination membranes, Proc.
Natl. Acad. Sci. U. S. A., 2018, 115, 8694–8699.
53 T. E. Culp, B. Khara, K. P. Brickey, M. Geitner, T. J. Zimudzi,
J. D. Wilbur, S. D. Jons, A. Roy, M. Paul,
B. Ganapathysubramanian, A. L. Zydney, M. Kumar and
E. D. Gomez, Nanoscale control of internal inhomogeneity
This journal is © The Royal Society of Chemistry 2021

Tutorial Review
enhances water transport in desalination membranes,
Science, 2021, 371, 72–75.
54 O. Coronell, B. J. Marinas, X. J. Zhang and D. G. Cahill,
Quantification of functional groups and modeling of their
ionization behavior in the active layer of FT30 reverse
osmosis membrane, Environ. Sci. Technol., 2008, 42,
5260–5266.
55 D. Chen, J. R. Werber, X. Zhao and M. Elimelech, A facile
method to quantify the carboxyl group areal density in the
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
active layer of polyamide thin-film composite membranes,
J. Membr. Sci., 2017, 534, 100–108.
Open Access Article. Published on 13 April 2021. Downloaded on 4/24/2023 5:23:13 PM.
56 R. Verbeke, A. Bergmaier, S. Eschbaumer, H. Mariën,
G. Dollinger and I. F. J. Vankelecom, Full elemental
depth-profiling with nanoscale resolution: The potential of
Elastic Recoil Detection (ERD) in membrane science,
J. Membr. Sci., 2019, 572, 102–109.
57 S. H. Kim, S.-Y. Kwak and T. Suzuki, Positron Annihilation
Spectroscopic Evidence to Demonstrate the Flux-
Enhancement Mechanism in Morphology-Controlled Thin-
Film-Composite (TFC) Membrane, Environ. Sci. Technol.,
2005, 39, 1764–1770.
58 T. Fujioka, N. Oshima, R. Suzuki, W. E. Price and
L. D. Nghiem, Probing the internal structure of reverse
osmosis membranes by positron annihilation spectroscopy:
Gaining more insight into the transport of water and small
solutes, J. Membr. Sci., 2015, 486, 106–118.
59 Q. Fu, N. Verma, H. Ma, F. J. Medellin-Rodriguez, R. Li,
M. Fukuto, C. M. Stafford, B. S. Hsiao and B. M. Ocko,
Molecular Structure of Aromatic Reverse Osmosis Polya-
mide Barrier Layers, ACS Macro Lett., 2019, 8, 352–356.
60 P. S. Singh and V. K. Aswal, Compacted Nanoscale Blocks To
Build Skin Layers of Reverse Osmosis and Nanofiltration
Membranes: A Revelation from Small-Angle Neutron
Scattering, J. Phys. Chem. C, 2007, 111, 16219–16226.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Chem Soc Rev
61 P. S. Singh, P. Ray, Z. Xie and M. Hoang, Synchrotron SAXS
to probe cross-linked network of polyamide ‘reverse osmo-
sis’ and ‘nanofiltration’ membranes, J. Membr. Sci., 2012,
421-422, 51–59.
62 X. Feng, Q. Imran, Y. Zhang, L. Sixdenier, X. Lu,
G. Kaufman, U. Gabinet, K. Kawabata, M. Elimelech and
C. O. Osuji, Precise nanofiltration in a fouling-resistant self-
assembled membrane with water-continuous transport
pathways, Sci. Adv., 2019, 5, eaav9308.
63 X. Zhou, Y.-Y. Zhao, S.-R. Kim, M. Elimelech, S. Hu and
J.-H. Kim, Controlled TiO2 Growth on Reverse Osmosis and
Nanofiltration Membranes by Atomic Layer Deposition:
Mechanisms and Potential Applications, Environ. Sci. Tech-
nol., 2018, 52, 14311–14320.
64 B. Liang, H. Wang, X. Shi, B. Shen, X. He, Z. A. Ghazi,
N. A. Khan, H. Sin, A. M. Khattak, L. Li and Z. Tang,
Microporous membranes comprising conjugated polymers
with rigid backbones enable ultrafast organic-solvent nano-
filtration, Nat. Chem., 2018, 10, 961–967.
65 T. Wei, L. Zhang, H. Zhao, H. Ma, M. S. J. Sajib, H. Jiang and
S. Murad, Aromatic Polyamide Reverse-Osmosis Membrane:
An Atomistic Molecular Dynamics Simulation, J. Phys.
Chem. B, 2016, 120, 10311–10318.
66 J. Muscatello, E. A. Müller, A. A. Mostofi and A. P. Sutton,
Multiscale molecular simulations of the formation and
structure of polyamide membranes created by interfacial
polymerization, J. Membr. Sci., 2017, 527, 180–190.
67 F. Foglia, S. Karan, M. Nania, Z. Jiang, A. E. Porter,
R. Barker, A. G. Livingston and J. T. Cabral, Neutron
Reflectivity and Performance of Polyamide Nanofilms for
Water Desalination, Adv. Funct. Mater., 2017, 27, 1701738.
68 V. Kolev and V. Freger, Hydration, porosity and water dynamics
in the polyamide layer of reverse osmosis membranes: A
molecular dynamics study, Polymer, 2014, 55, 1420–1426.
Chem. Soc. Rev., 2021, 50, 6290–6307 | 6307